Donghua Wang

Porous silicon (PSi), characterized by its high specific surface area and highly tunable morphology, presents significant potential across optoelectronics, energy storage, and biomedical applications. This review provides a systematic analysis of the synthesis methodologies, interfacial chemical engineering, and diverse applications of PSi. Initially, fabrication techniques are examined, contrasting the pore formation mechanisms of electrochemical anodization, metal-assisted chemical etching (MACE), and emerging vapor-phase etching methods, while elucidating the control of geometric parameters from microporous to macroporous scales. To address the thermodynamic instability of the hydride-terminated surface, this review systematically evaluates modification strategies such as thermal oxidation, hydrosilylation, carbonization, and atomic layer deposition (ALD). We critically analyze their efficacy in mitigating oxidative drift and enabling specific functionalization. Subsequently, the review summarizes current applications in sensing (refractive index and photoluminescence modulation), energy storage (lithium-ion battery anodes and supercapacitors), and microsystem technologies (radio frequency (RF) isolation, gettering, and micro-electro-mechanical systems (MEMS) sacrificial layers), emphasizing the critical role of structure–property relationships. Finally, an objective assessment is provided regarding the challenges in translating PSi technology to industrial scales, specifically addressing the trade-offs between biodegradability and stability, wafer-scale process uniformity, and the compatibility of wet-chemical processing with standard complementary metal–oxide–semiconductor (CMOS) integration flows.